This invention pertains generally to an improved method for producing controlled phase metal alloy powders and particularly to a method of preparing single phase magnesium-based alloys for engineering and hydrogen storage applications.
Increasing demands for improved performance, especially in aerospace and automotive systems, have focused attention on enhancing material properties. Where weight considerations are at a premium the use of low density materials is essential. This is particularly true in the aircraft and automobile industries where light weight coupled with strength and formability are desired, here magnesium alloys are used to produce strong, lightweight parts. In addition to the engineering applications of magnesium alloys there are important specialized applications, hydrogen storage, for example, that make use of magnesium's unique properties. Single phase intermetallic alloys are especially desirable for these applications. However, these alloys pose special problems when traditional metallurgical fabrication procedures are employed.
Metal alloys are typically fabricated by melting together the constituents, which have been previously combined in the proper ratio, or combining the separate molten constituents in the proper proportion to produce the alloy composition desired, or by adding alloying metals to a molten master batch. These traditional processes suffer from several disadvantages, particularly with regard to preparing single phase alloys. Included among these is the tendency to form local compositional inhomogeneities, segregation, formation of undesired intermetallic compounds, lack of elemental interdiffusion and generally, the inability to control grain size and microstructure on a submicrometer basis. Magnesium containing alloys pose special problems because of the large differences in melting temperatures between magnesium and other metals used to alloy with magnesium as well as the significant vapor pressure of magnesium at temperatures even as low as 300.degree. C.
One approach to producing single phase magnesium alloys has been the use of rapid solidification. Here, various atomization techniques are used to produce magnesium alloy powders. These powders are then consolidated by compaction or extrusion. The mechanical properties of the extruded material have been observed to be superior to magnesium alloys produced by conventional processes owing to structural refinements and the small grain size of the rapidly solidified particulate material. Substantial increases in longitudinal tensile strength and impact strength have been observed as compared to the same alloy extruded from conventional ingot material. Further, the ability to control grain size and microstructure on the submicrometer scale can provide additional structural applications for magnesium alloys and can enhance the potential for employing other metal forming techniques such as superplastic forming. On the other hand, there are numerous drawbacks associated with rapidly solidified magnesium alloys, in particular alloys produced by gas atomization, including non-uniformity of powder particle size, a high proportion of highly inflammable and adherent fines and the need to filter, clean and recycle large volumes of atomizing gas.
In addition to the utility of single phase magnesium alloys for engineering applications as set forth above, there is another important application of these magnesium alloys, hydrogen storage.
Growing energy needs coupled with the realization that supplies of conventional energy sources are not only not inexhaustible but also are becoming more costly have prompted the recognition that hydrogen can be used as an energy source. Hydrogen can be used as a fuel for internal combustion engines in place of hydrocarbons. It can also be used to fuel hydrogen-air fuel cells for the production of electricity. However, one of the problems posed by the use of hydrogen is its transportation and storage for which a number of solutions have been proposed. Among these are:
Storage under high pressure in steel cylinders. This method of storing hydrogen has the disadvantages of requiring storage of a hazardous gas under high pressure and the use of heavy containers which are difficult to handle. PA1 Storage under cryogenic conditions entails not only the use of heavy containers but also the use of expensive and potentially hazardous cryogenic liquids. PA1 Storage as a chemical compound, a hydride. In this case, hydrogen is released when required by simply decomposing the hydride either by lowering the pressure or heating the hydride, or both.
The storage of hydrogen as a hydride is well known in the art and numerous systems have been described wherein hydrogen is stored as an interstitial hydride or as a stoichiometric compound of the appropriate metal; the hydrogen then being released as required. Metal hydrides have the added advantage that they are reversible hydrogen storage systems. Of the various metals and metal alloys that form hydrides useful for hydrogen storage iron-titanium, lanthanum-nickel, vanadium, palladium and magnesium are the most popular.
Magnesium is the most useful of the hydride-forming metals because of its relatively low cost and light weight which allows for a theoretical capacity of 7.6% by weight of hydrogen. However, the use of the Mg/MgH.sub.2 system for the reversible storage of hydrogen on a large scale poses several practical problems. For example, in order to have the maximum specific surface area for hydrogen absorption and thus for the conversion to MgH.sub.2, the magnesium should be in the form of a powder. Magnesium powder having a high surface area can be produced by thermal decomposition of the hydride. The hydride can be produced initially by absorbing hydrogen onto magnesium at elevated temperature and pressure for a period of about six hours. This process can be repeated until magnesium powder of the desired size (or surface area) is produced. However, by most economic criteria, the cost of the MgH.sub.2 prepared by these indirect techniques is too high to permit economical use of the magnesium powder thus obtained for the storage of hydrogen in the form of a hydride. Moreover, magnesium powders present serious handling and safety problems. Magnesium turnings, while not presenting the safety and handling problems of magnesium powder, have significant disadvantage as hydrogen storage materials namely, very severe hydriding conditions are required in order to convert turnings to MgH.sub.2 thus rendering the use of turnings impractical notwithstanding the lower costs and other advantages associated with the use of this material.
The use of magnesium for the storage of hydrogen as a hydride is not entirely satisfactory due to the fact that a temperature of about 400.degree. C. is required to decompose the hydride. These severe conditions lessen the practical use of magnesium metal and its hydride as a means of storing hydrogen. Moreover, because of its chemical reactivity metallic magnesium will rapidly oxidize in the presence of air and/or water vapor to form stable MgO or MgO surface layers. In order for hydrogen to be incorporated into bulk magnesium as MgH.sub.2 it is necessary that the hydrogen molecules present on the magnesium surface be dissociated into hydrogen atoms. However, surface layers of MgO can inhibit the dissociation of hydrogen molecules into atomic hydrogen on the magnesium metal surface and the adsorption of the hydrogen atoms and their migration into bulk magnesium metal. Associated with the formation of surface layers is the fact that the hydrogen capacity of magnesium diminishes with cycling. As the number of decomposition-reconstitution cycles increases, the amount of hydrogen that can be taken up by the magnesium decreases.
It is desirable to provide conditions wherein the conversion ratio of MgH.sub.2 /Mg is as high as possible in order to obtain the best utilization of magnesium. That is, the molar ratio MgH.sub.2 /Mg should be as high as possible while the time required for absorption and desorption of hydrogen should be as low as possible and both the absorption temperature and pressure should likewise be as low as possible. The absorption temperature and pressure, the time required for complete hydrogenation of magnesium and the decomposition temperature and pressure can be reduced by providing a catalytic surface that serves to expedite the dissociation of molecular hydrogen into atomic hydrogen. It is known in the art that these catalytic surfaces are preferably alloys. The disadvantage of magnesium alloys for the purposes described is, as set forth above, that they are comparatively costly since they must be prepared by melting the elemental components together, casting the resulting melt and milling or grinding the cast body to a fine powder capable of absorbing hydrogen.
The prior art discloses numerous attempts both to improve the hydrogen storage capacity of magnesium as well as to overcome the difficulties associated with hydriding/dehydrding magnesium. U.S. Pat. No. 4,200,623 discloses the preparation of hydrogen storage systems by mixing together magnesium metal powder and a powder selected from at least one of groups IA, IIIB, IVB, VIB, VIIB and VIII, compacting the mixture and then hydrogenating the compacted mixture by heating in hydrogen at temperatures between 400.degree. C. and 1600.degree. C. U.S. Pat. No. 4,402,933 describes a method of hydrogen storage, wherein magnesium powder is intimately mixed, e.g., by ball milling, with powders selected from the group consisting of inert metals, metal alloys, metal oxides, carbides and nitrides. The mixture is then hydrogenated by heating in hydrogen, typically at high pressure (.apprxeq.30 bar) for about 15 hrs. at between 350.degree. C. and 400.degree. C. U.S. Pat. No. 4,613,362 discloses a method for hydrogen storage that employs an magnesium/iron granulate, wherein the iron content is between 1% and 20% by weight. Hydrogen charging of the magnesium/iron granulate takes place at a constant pressure of 1.5 MPa and a temperature of 400.degree. C. U.S. Pat. No. 4,537,761 discloses a hydrogen storage system comprising magnesium alloys, preferably Mg/Cu alloys, that are subjected to a plurality of sequential activating cycles at elevated temperatures and hydrogen gas pressures. The purpose of the plurality of hydrogenation/dehydrogenation cycles is to produce a magnesium alloy having a high surface area, thereby more readily promoting hydrogenation of the magnesium alloy. While the prior art recognized the advantage magnesium alloys offered in overcoming problems associated with hydrogenation/dehydrogenation of magnesium metal, as set forth above, the solutions disclosed were either to start with expensive magnesium alloys that can contain local compositional inhomogeneities, segregation, undesired intermetallic compounds, and/or uncontrolled grain size; to employ elaborate fabrication steps to prepare the desired alloy that, because of lack of control of the fabrication step(s), are not capable of producing a preferred single phase alloy; or to subject the alloy to a plurality of time consuming and uneconomic hydrogenation/dehydrogenation cycles, generally at high pressure, in order to provide sufficient reactive surface.
Thus, there is a continuing need for an inexpensive method of producing controlled and preferably single phase metal alloy powders, particularly single phase magnesium-based alloy powders, useful for engineering and hydrogen storage applications. It is desirable that the powders that are a product of this method require no further processing and further, that the alloy powders possess a catalytic surface for the dissociation of molecular hydrogen into atomic hydrogen.
Responsive to these needs, a novel method for preparing single phase alloy metal powders, particularly magnesium-based alloy metal powders, is disclosed herein. The advantages of this novel method of preparing alloy metal powers are severalfold. First the product produced by this process is a single phase alloy. Second, the product, is a powder, therefore, the expensive operations involved in reducing an ingot or cast product to a powder are eliminated. Third, the particle size distribution of the final product can be fixed by the powder chosen as the other component of the alloy. Fourth, by virtue of the smaller grain size, the mechanical properties of the alloys produced by the present invention possess superior properties. Fifth, the alloy powder can be fabricated into desired shapes by standard powder metallurgical techniques. All these aspects of the present invention for producing single phase alloys lend much greater control over the final product.